Conversion of oils with amounts of oxygen insufficient for complete combustion for the formation of carbon monoxide and hydrogen



M y 1963 HT NONNENMACHER ETAL 3,

CONVERSION OF OILS WITH AMOUNTS 0F OXYGEN INSUFFICIENT FOR COMPLETECOMBUSTION FOR THE FORMATION OF CARBON MONOXIDE AND HYDROGEN Filed Sept.4, 1957 lNVENTORS HELMUT NONNENIVIACHER ERNST BARTHOLOME ATT'YS UnitedStates Patent Office 3,090,634 Patented May 21, 1963 CGNVERSIGN F OILSWITH AMOUNTS OF OXY- GEN INSUFFICIENT FOR COMPLETE COMBUS- TION FGR THEFORMATION OF CARBON MONOXIDE AND HYDROGEN Heimut Nonnenmacher,Ludwigshafen (Rhine), and Ernst Bartholom, Heidelberg, Germany,assignors to Badische Anilin- & Soda-Fahrik Aktiengesellschaft,Ludwigshafen (Rhine), Germany Filed Sept. 4, 1957, Ser. No. 681,945iaims priority, application Germany Sept. 8, 1956 3 Claims. (Cl. 48-212)This invention relates to a process for the production of carbonmonoxide and hydrogen by reacting oils with amounts of oxygeninsufficient for complete combustion.

It is known to convert liquid hydrocarbons together with oxygen and, ifdesired, steam into carbon monoxide and hydrogen in a bed of fluidizedsolid substances at high temperatures. In this method the liquidhydrocarbons are sprayed into the fluidized layer and theoxygen-containing gas is led upwardly through the fluidized layer. Thedisadvantage of this method of operation consists in the fact that evenwhen using highly active catalysts and temperatures of more than 1000"C. it is not possible in continuous operation to obtain a synthesis gaswith a low content of hydrocarbons. Moreover, troublesome and expensivedistributor devices are necessary in an industrial plant in order todistribute the liquid hydrocarbon uniformly over the fluidized mass andto avoid a breakthrough of oxygen or the formation of soot. Furthermore,the catalyst is impaired in its activity by coking and, especially whenoils with non-vaporizable components are being worked up, deactivatedrelatively rapidly by the impurities introduced with the liquidhydrocarbons so that a high consumption of catalyst must be accepted.

We have now found that the said disadvantages are avoided by carryingout in three stages the conversion of oirs containing unvaporizablecomponents, especially mineral oils or their fractions or residues, withamounts of oxygen insufiicient for complete combustion, by contact withfluidized catalysts.

In the first stage, the hydrocarbon mixture is separated by thermaltreatment into a vaporous and a non-vaporous fraction. The kind ofthermal treatment depends on the initial material. As a rule it iscarried out so that in the first stage more than one third, preferablymore than one half, advantageously more than two-thirds of the initialmaterial forms a vaporous fraction. In the case of mineral oils andmineral oil residues, which contain a considerable proportion ofvaporizable hydrocarbons, a distillation is usually sufiicient, ifnecessary in the presence of steam, at temperatures up to about 380 C.In the case of mineral oil residues of higher boiling point, the firststage can consist of a so-called destructive pressure distillation, i.e.a mild thermal decomposition under pressure, at temperatures of about400 to 530 C., the residence times being kept so short thatsubstantially only vaporous and liquid products are formed. In the caseof mineral oil residues of very high boiling point and poor in hydrogen,and in the case of tars, pitches and similar substances, the first stageconsists of a thermal cracking to vaporous products and coke attemperatures of 400 to 600 C. and long residence times.

In the second stage, the non-vaporous fraction obtained in the firststage is reacted in a flame with oxygen and if desired steam and/orcarbon dioxide. If the non-vaporous fraction from the first stage isliquid, it is preferable to atomize it with the oxygen-containing gasesand if desired steam and/or carbon dioxide as propellant in a two-fluidnozzle, to ignite the mixture and to react it in a flame. If on theother hand the products of the first stage are vaporous products andcoke, it is preferable to grind the coke and to react it in dust formwith the oxygen and the endothermic gasifying agents in a flame.

The amount of oxygen to be introduced in the second stage for eachkilogram of non-vaporous components is dependent on the relative amountof this fraction in relation to the whole of the hydrocarbon mixture andis preferably greater the smaller this relative proportion is. At least0.9 ch. 111. (cubic meter) (normal temperature and pressure), preferably1.2 cb. m. of oxygen per kilogram of non-vaporous fraction is used. Ifin the first stage more than one third of the initial material forms avaporous fraction, at least 0.9 cb. m. of oxygen per kilogram ofnon-vaporous fraction is used. if the vaporous fraction is more than onehalf, at least 1.2 eh. m. is used, and if the vaporous fraction is morethan two-thirds of the initial material, at least 1.5 cb. m. of oxygenper kilogram of non-vaporous fraction is used. If the nonvaporousfraction amounts to a maximum of 25% by weight of the hydrocarbonmixture, it is advantageous to use an amount of oxygen at leastsufficient for the complete combustion of this fraction. Slightformation of carbon black which sometimes occurs can be substantially orcompletely prevented by introducing continuously or periodically intothe second stage compounds of the elements of the first and/ or secondgroup of the periodic system and/or of the metals of the iron group. Ifthe non-vaporous fraction is liquid it is preferable to dissolve thereinoil-soluble compounds of the said kind.

In the third stage the hot reaction products of the second stage and thevaporous fraction from the first stage are introduced, separately ortogether, if desired with further amounts of oxygen, steam and/or carbondioxide, into a fluidized layer of catalyst and reacted therein tocarbon monoxide and hydrogen without external supply of heat attemperatures of about 700 to 1200 C., especially about 800 to l0O0 C.The reaction mixture flows upwardly through the fluidized layer. It hasbeen found that the inorganic constituents entrained by the reactiongases from the second stage and originating from the compounds added inthe second stage or being contained in the initial materials, and alsoany carbon black formed in the second stage and carried through to thethird stage, do not impair the catalytic reaction of the third stage orshorten the life of the catalyst.

The process as a rule is carried out at atmospheric or reduced pressurein the third stage. In many cases, however, it is advantageous to use anincreased pressure, for example of 2 to about 30 atmospheres. Ascatalysts there are suitable for example refractory porous materials,such as magnesite and siliceous materials, which are provided with oneor more metals of the 8th group of the periodic system, especiallynickel. Mineral oils, and also their fractions, residues or conversionproducts, for example cracking or hydrogenation products are most oftenused as starting materials.

The invention will now be further described in the following examplewith reference to the accompanying drawing which shows diagrammaticallyan apparatus suitable for carrying out the invention. The invention isnot limited to the said apparatus or to the process now to be described.

Example Through pipe 1 190 kilograms of a paraffin-based petroleum andthrough pipe 2 kilograms of steam are introduced per hour into apreheater 3 and heated up therein to about 380 C. The mixture thenpasses into a distillation column 4 from which 143 kilograms per hour ofvaporous hydrocarbons pass together with the steam through pipe 7 and 47kilograms of liquid residue run oil? from the bottom through pipe 5. Theliquid residue is forced by the pump P into a two-fluid atomizer nozzle6 and atomized with 124 N cb. m. (normal temperature and pressure) ofoxygen and 72 kilograms of steam per hour, introduced through pipes 8and 9. The atomized mixture is reacted in a flame reaction in acombustion chamber 10 and the hot reaction gases and vapors are suppliedto the lower conical part of a fluidized layer chamber 11, thecross-section of which in the cylindrical part amounts to 2 squaremeters.

The vaporous fraction flowing through the pipe 7 is also introduced intothe lower conical partrof the fluidized layer chamber 11. The fluidizedlayer consists of a finely-grained magnesite-nickel catalyst containingabout 10% by Weight of nickel. A reaction temperature of about 1000 C.is set up therein without the supply of heat from outside. The reactiongases leaving the fluidized layer are freed in a cyclone 12 from thebulk of the entrained solid substances. These are supplied to thefluidized layer again through pipe 15.

About 600 eh. m. ((normal temperature and pressure) of carbon monoxideand hydrogen per hour are obtained. The reaction gas freed from Wateralso contains a few percent of C small amounts of nitrogen,sulphur-containing compounds and less than 0.3% by volume ofhydrocarbons in the form of methane.

The catalysthas a life of several months. It can be withdrawn throughpipe 13 and replenished from vessel 14.

We claim:

1. A process for the production of a gas consisting essentially ofcarbon monoxide and hydrogen from mineral oils wherein said mineral oilsare reacted with amounts of oxygen which are insufficient for completecombustion which process comprises:

(1) thermally treating said mineral oil to separate the oil into avaporous and a nonvaporuos fraction, the vaporous fraction constitutingmore than one-third by weight of the total,

(2) reacting the nonvaporous fraction in a flame (a) with at least 0.9cubicrneter of oxygen per kilogram of the nonvaporous fraction wheresaid vaporous fraction is up to one-half by weight of the total initialmaterial,

(12) with at least 1.2 cubic meters of oxygen per kilogram of thenonvaporous fraction where said vaporous fraction is more than one-halfand up to two-thirds by weight of said total initial material, and

(c) with at least 1.5 cubic meters of oxygen per kilogram of thenonvaporous fraction where said vaporous fraction is more thantwo-thirds by weight of the total initial material, said quantities ofoxygen being measured at normal temperature and pressure, and

(3) thereafter leading the substances thus formed in said nonvaporousfraction-oxygen reaction and said vaporous fraction simultaneously intoa fluidized layer of reaction catalyst at a temperature of from about700 to 1200 C. wherein a further reaction takes place between saidmineral oil and oxygen and whereby a synthesis gas is producedconsisting essentially of carbon monoxide and hydrogen.

2. A process as in claim 1 wherein the reaction catalyst is selectedfrom the group consisting of porous refractory materials and siliceousmaterials, which materials contain at least one metal of the 8th groupof the periodic system.

3. A process as in claim 2 wherein the said vaporous fraction is atleast by weight of the said oil, and wherein said nonvaporous fractionis burned with an amount of oxygen at least sufiicient for completecombustion.

References Cited in the file of this patent UNITED STATES PATENTS HaneyNov. 10, 1959

1. A PROCESS FOR THE PRODUCTION OF A GAS CONSISTING ESSENTIALLY OFCARBON MONOXIDE AND HYDROGEN FROM MINERAL OILS WHEREIN SAID MINERAL OILSARE REACTED WITH AMOUNTS OF OXYGEN WHICH ARE INSUFFICIENT FOR COMPLETECOMBUSTION WHICH PROCESS COMPRISES: (1) THERMALLY TREATING SAID MINERALOIL TO SEPARATE THE OIL INTO VAPOROUS AND A NONVAPOROUS FRACTION, THEVAPOROUS FRACTION CONSTITUTING MORE THAN ONE-THIRD BY WEIGHT OF THETOTAL, (2) REACTING THE NONVAPOROUS FRACTION IN A FLAME (A) WITH ATLEAST 0.9 CUBIC METER OF OXYGEN PER KILOGRAM OF THE NONVAPOROUS FRACTIONWHERE SAID VAPOROUS FRACTION IS UP TO ONE-HALF BY WEIGHT OF THE TOTALINITIAL MATERIAL, (B) WITH AT LEAST 1.2 CUBIC METERS OF OXYGEN PERKILOGRAM OF THE NONVAPOROUS FRACTION WHERE SAID VAPOROUS FRACTION ISMORE THAN ONE-HALF AND UP TO TWO-THIRDS BY WEIGHT OF SAID TOTAL INITIALMATERIAL, AND (C) WITH AT LEAST 1.5 CUBIC METERS OF OXYGEN PER KILOGRAMOF THE NONVAPOROUS FRACTION WHERE SAID VAPOROUS FRACTION IS MORE THANTWO-THIRDS BY WEIGHT OF THE TOTAL INITIAL MATERIAL, SAID QUANTITIES OFOXYGEN BEING MEASURED AT NORMAL TEMPERATURES AND PRESSURE, AND (3)THERAFTER LEADING THE SUBSTANCES THUS FORMED IN SAID NONVAPOROUSFRACTION-OXYGEN REACTION AND SAID VAPOROUS FRACTION SIMULTANEOUSLY INTOFLUIDIZED LAYER OF REACTION CATALYST AT A TEMPERATURE OF FROM ABOUT 700*TO 1200*C. WHEREIN A FURTHER REACTION TAKES PLACE BETWEEN SAID MINERALOIL AND OXYGEN AND WHEREBY A SYNTHESIS GAS IS PRODUCED CONSISTINGESSENTIALLY OF CARBON MONOXIDE AND HYDROGEN.